Rh(iii)-catalyzed oxidative C-H bond arylation with hydroquinones: Sustainable synthesis of dibenzo[b,d]pyran-6-ones and benzo[d]naphtho[1,2-b]pyran-6-ones

Article abstract of DOI:10.1039/c4cc08260e

An efficient Rh(iii)-catalyzed C-H bond arylation with phenol derivatives was developed for the direct and sustainable synthesis of dibenzo[b,d]pyran-6-ones and benzo[d]naphtho[1,2-b]pyran-6-ones. This reaction shows good substrate scope and excellent fun

Full text of DOI:10.1039/c4cc08260e

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COMMUNICATION
Rh(III)-catalyzed oxidative C−H bond arylation with hydroquinones: sustainable synthesis of
dibenzo[b,d]pyran-6-ones and benzo[d]naphtho[1,2-b]pyran-6-ones†
Wei Yang, Shan Wang, Qian Zhang, Qun Liu and Xianxiu Xu*
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
5
DOI: 10.1039/b000000x
An efficient Rh(III)-catalyzed C−H bond arylation with
phenol derivatives was developed for the direct and
sustainable synthesis of dibenzo[b,d]pyran-6-ones and
benzo[d]naphtho[1,2-b]pyran-6-ones. This reaction shows
good substrate scope and excellent functional group
compatibility and gives the products in good yields with
excellent chemoselectivity.
1
0
The dibenzo[b,d]pyran-6-one (benzo[c]chromen-6-one) and
benzo[d]naphtho[1,2-b]pyran-6-one structural motifs consist of
the core of many natural products with pharmacological
1
2
2
3
3
4
5
0
5
0
5
0
1
2
3
4
relevance,
such as fasciculiferol, alternariol, autumnariol,
4
5
6
autumnariniol, altenuisol, gilvocarcins M,
ravidomycin, chrysomycins A, B and C, and arnottin I (Fig. 1).
Structurally, the dibenzo[b,d]pyran-6-one and
E
and V,
7
8
9
benzo[d]naphtho[1,2-b]pyran-6-one derivatives share a biaryl
fragment. While a number of synthetic methods for the
construction of these frameworks have been reported through the
Fig. 1 Some natural products possessing dibenzo[b,d]pyran-6-one or
benzo[d]naphtho[1,2-b]pyran-6-one core structures.
1a,3-7,9,10
45 to form the new C−C bonds whereas the C−H bonds of the
phenols remain intact. In recent years, the Rh(III)-catalyzed C−H
activation has received significant interest, particularly for C−C
intra- or inter-molecular biaryl formation as key step,
the
development of conceptually distinct synthetic approaches,
especially those meeting the requirements of green and
sustainable chemistry, is still of great interest.
1
4
and C−N bond formation, but direct arylation to form a biaryl
structural motif via Rh(III)-catalyzed C−H bond functionalization
Recently, transition-metal-catalyzed direct oxidative C−H bond
arylation has emerged rapidly as an efficient and straightforward
15
5
0
is less explored. Only a few examples were reported by using
1
1
synthetic protocol for the construction of biaryls. This strategy
obviates prefunctionalization of the starting materials, thus
dramatically improving the overall efficiency in an atom- and
step-economical manner for C−C bond formation. Among the
wide variety of arylating reagents used in these reactions, phenol
derivatives, such as aryl carbamates, phosphates or sulfamates,
are promising coupling partners for the construction of C−C bond
because they are often readily available and inexpensive (Scheme
(a) C H bond/C OR bond functionalization: Prior work
R2
R2
cat. [TM]
H
+ RO
R1
R1
(
b) C H bond/C OH bond functionalization: Prior work
R2
cat. [Ru]
R2
H
+ HO
R1
R1
1
2
(c) C H bond/C H bond functionalization with phenols: This work
1
a). With respect to the step economy, in 2012, Ackermann and
OH
OMe
O
O
co-workers developed a ruthenium-catalyzed formal dehydrative
direct arylations by employing phenols as proelectrophiles in a
H
cat. [Rh]
NH
OH
OMe
N
R1
+
H
R1
1
3
non-sequential fashion (Scheme 1b). In these phenol derivatives
R2
H
OH
O
participated transformations, the C−O bonds are usually cleaved
R2
OH
intramolecular
lactonization
O
R1
two natural product
Department of Chemistry, Northeast Normal University, Changchun
frameworks formation
atom- and step-enconomy
1
30024, China. Fax: 86 431 85099759; Tel: 86 431 85099759
E-mail: xuxx677@nenu.edu.cn
Electronic Supplementary Information (ESI) available: Experimental
R2
OH
†
Scheme 1 Strategies for biaryl synthesis and for dibenzo[b,d]pyran-6-one
and benzo[d]naphtho[1,2-b]pyran-6-one synthesis.
details and spectral data for 3, 4, 7 and 8 are included in the supporting
information. For ESI data see DOI: 10.1039/b000000x/
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 1

ChemComm
Page 2 of 4
1
5a-c
15d,e
arylhalides
,
heteroarenes
,
4-hydroxycyclohexa-2,5-
donating and electron-withdrawing groups at the para position of
1
5g
15h
dienones , and Arylsilanes as arylating reagents. Herein we
aryl groups participated well in this reaction and the
View Article Online
report a Rh(III)-catalyzed chemoselective oxidative C−H bonds
corresponding products were obtained in good to excellent yields
DOI: 10.1039/C4CC08260E
arylation with phenols (Scheme 1c). This biaryl formation and 40 (3a–h). meta-Substituted benzamides also smoothly reacted to
5
0
5
0
5
lactonization cascade offers a new and sustainable process for the
give the corresponding dibenzo[b,d]pyran-6-ones 3j and 3k in
good yields and in a highly regioselective manner. However, the
ortho-methyl-substituted benzamide reacted slowly and gave the
product 3i in lower yield. The arylation reaction of 3,4-dimethyl-
1
6
rapid
benzo[d]naphtho[1,2-b]pyran-6-ones.
Initially, the reaction of N-methoxybenzamide 1a with
synthesis
of
dibenzo[b,d]pyran-6-ones
and
hydroquinone 2a was employed to screen the reaction conditions 45 subsitituted benzamides also smoothly proceeded to give the
for the C−H bond arylation (Table 1). When the reaction was
conducted in DCE (1,2-dichloroethane) in the presence of
1
1
2
2
corresponding products 3l in high yield, while the reaction of 3,5-
dimethyl-subsitituted benzamides does not occur (3m). -
naphthamide also produced the corresponding 2-hydroxy-6H-
naphtho[2,3-c]chromen-6-one 3n in good yield. Heteroarylamide,
[
(
Cp*RhCl2]2 (2.5 mol%), CsOAc (30 mol%), iodosylbenzene
PhI=O, 200 mol%) and 0.5 equivalent of acetic acid at 90 C for
o
1
0 h, 2-hydroxy-6H-dibenzo[b,d]pyran-6-one 3a was obtained in 50 such as N-methoxythiophene-2-carboxamide also afforded the
57% yield (Table 1, entry 1). Solvent screening revealed that the
reaction in acetone gave similar result (Table 1, entry 6 vs entries
product 8-hydroxy-4H-thieno[2,3-c]chromen-4-one 3o in high
yield. It was worth mentioning that a wide range of important
functional groups on the aryl moieties of benzamides 1, such as
methoxy, chloro, iodo and trifluoromethyl groups, were well
2
-5). To our delight, when a mixture of DCE and acetone (1:1)
was used as solvent, the yield of 3a was improved to 98% (Table
1
, entry 7). Decreasing the amount of 2a to 1.5 equivalents or 55 tolerated under the reaction conditions (3e–h and 3k).
o
conducting the reaction at 70 C resulted in lower yield of 3a
Table 1, entries and 9). Other oxidants, such as
iodobenzenediacetate (PIDA) lead to poor yield (Table 1, entry
0), and [I,I-bis(trifluoroacetoxy)-iodo]benzene (PIFA) does not
Table 2 The scope of N-methoxyarylamides 1
(
8
O
O
OH [Cp*RhCl2]2 (2.5 mol%)
1
CsOAc (30 mol%)
HOAc (50 mol%)
R1
O
OMe
R1
N
+
give any desired product 3a (Table 1, entry 11). In the absence of
oxidant the desired product 3a could not be detected (Table 1,
entry 12). The use of stronger acid such as
trifluoromethanesulfonic acid completely inhibited the reaction
H
PhI=O (200 mol%)
DCE/Acetone, 90 o
C
OH
2a
1
3
OH
3
a, R = H, 5 h, 98%
b, R = Me, 6 h, 95%
c, R = Et, 7 h, 81%
O
(
entry 13), whereas, in the absence of acetic acid product 3a was
O
3
3
3
3
3
3
3
O
obtained in moderate isolated yield (Table 1, entry 14).
O
t
d, R = Bu , 6 h, 75%
a
3
0
Table 1 Optimization of reaction conditions
R
e, R = MeO, 11 h, 85%
f, R = Cl, 6 h, 61%
g, R = I, 8 h, 51%
OH
OH
3
i, 22 h, 35%
h, R = CF , 11 h, 57%
3
O
O
O
O
MeO
O
O
O
O
OMe
OH
entry
solvent
oxidant
additive
Time
h)
Yield
(%)
b
OH
OH
OH
(
1
2
3
4
5
6
7
DCE
DCM
MeOH
PhI=O
PhI=O
PhI=O
PhI=O
PhI=O
PhI=O
PhI=O
PhI=O
PhI=O
PIDA
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
HOTf
10
10
10
5
5
7
57
31
trace
35
0
55
98
66
75
40
0
3j
77
3k 3k'
3l
,
6 h,
%
,
, 6 h, 98% (2.4:1)
, 11 h, 81%
O
O
O
S
CH
3
CN
O
O
O
DMF
Acetone
c
DCE/Acetone
5
d
8
9
DCE/Acetone
DCE/Acetone
DCE/Acetone
DCE/Acetone
DCE/Acetone
DCE/Acetone
DCE/Acetone
15
15
10
10
10
10
10
OH
3m, 11 h, NR
OH
OH
e
3n, 6 h, 43%
3o, 8 h, 72%
a
b
1
1
1
1
1
1
0
1
2
3
4
Reactions conducted on 0.2 mmol scale. By H NMR spectroscopy.
PIFA
0
0
61
The Rh(III)-catalyzed C−H bond arylation/lactonization
PhI=O
PhI=O
6
0
cascade mentioned above (Table 1 and 2) represents a very
simple and highly efficient methodology for the direct synthesis
of the dibenzo[b,d]pyran-6-ones from readily available precursors
in an atom- and step-economical manner. To test the scope of the
arylating reagent, the domino reactions of selected phenol
a
Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), additive (0.1
mmol), solvent (2 mL). Isolated yields. The ratio of DCE and acetone
is 1:1 (v : v). 1.5 equiv of 2a was used. At 70 C.
b
c
d
e
o
With the optimal conditions in hand (Table 1, entry 7), we first
surveyed various N-methoxyarylamides 1 to determine the scope
of the reaction. Under these conditions, the reactions proceeded
smoothly to afford an array of dibenzo[b,d]pyran-6-ones in good
to excellent yields (Table 2). Substrates with both electron-
6
5
derivatives with N-methoxyarylamides
1
were further
investigated and the results were shown in Table 3. Under the
aforementioned optimal conditions (Table 1, entry 7) the
reactions of N-methoxybenzamide 1a with 2-methylbenzene-1,4-
diol 2b afforded the corresponding dibenzo[b,d]pyran-6-ones in
3
5
2
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high yield with regioisomers (3p and 3p') in a ratio of
approximately 1.1:1. The regioselectivity could be improved
when the bulky tert-butyl substituted benzene-1,4-diol 2c was
employed as arylation reagent ( the regioisomers 2-hydroxy-4-
tert-butyl-6H-benzo[c]chromen-6-one 3q and 2-hydroxy-3-tert-
butyl -6H-benzo[c]chromen-6-one 3q' were resulted in a ratio of
View Article Online
DOI: 10.1039/C4CC08260E
5
0
5
5
.3:1). The structure of the dominant product 3q was further
1
1
confirmed by two-dimensional H- H COSY spectroscopy (for
details, see the Supporting Information). Furthermore, when
naphthalene-1,4-diol 2d was used as an arylation agent, the
tetracyclic benzo[d]naphtho[1,2-b]pyran-6-ones 4a-c were
produced in good to high yields. The reaction of N-
methoxybenzamide 1a and phenol was also examined under these
conditions, but the desired dibenzo[b,d]pyran-6-one product
could not be detected.
1
benzoquinone (produced by oxidation of hydroquinone 2a with
PhI=O) affords intermediate B, which undergoes migratory
insertion into the incipient Rh−C bond to form seven-membered
1
7
1
5g,18
1
45 rhodacycle C.
Protonolysis and aromatization deliver biaryl
a
intermediate D concomitantly realeasing the catalyst Cp*RhX .
Metal or acid catalyzed nucleophilic substitution reaction occurs
2
Table 3 the scope of phenol derivatives 2
to furnish the final product 3a with the release of a O-methyl
1
9
hydroxamine.
O
OMe
N
3
+
a
H
1a
OH
NH2OMe
Cp*RhX2
HO
D
2
HX
2
HX
O
OMe
O
N
Rh Cp*
N
OMe
RhCp*
A
O
O
O
O
C
N OMe O
Rh
Cp
O
PhI=O
*
2a
a
b
1
50
B
O
Reactions conducted on 0.2 mmol scale. By H NMR spectroscopy.
Scheme 1 Proposed mechanism for the formation of 3a.
Finally, in order to highlight the synthetic potential of this new
strategy, two possible transformations of the generated hydroxyl-
substituted benzo[c]chromen-6-one were conducted (Scheme 2).
2-hydroxy-6H-dibenzo[b,d]pyran-6-one 3a was readily converted
During the studies of this Rh(III)-catalyzed C−H bond
2
2
3
3
4
0
5
0
5
0
arylation/lactonization cascade reaction of N-methoxyarylamides
with hydroquinone 2a, benzoquinone was detected by TLC in
the most cases. Since hydroquinone 2a is readily converted to
1
5
5
1
7
to the 2-hydroxy-6H-dibenzo[b,d]pyran-6-one triflate
triflation with Tf O in high yield. Reductive cleavage of the O-
triflate group with Pd(PPh and HCOOH provided the 6H-
6 by
benzoquinone by oxidation and the Rh(III) catalyzed insertion
2
of arene C−H bonds into α,β-unsaturated ketones was recently
1
8
3 4
)
realized, it is conceived that benzoquinone may be the coupling
partner in this Rh(III)-catalyzed reaction. To address this issue,
dibenzo[b,d]pyran-6-one 7 in high yield. Furthermore, Suzuki
coupling reaction of triflate 6 with 4-methylphenylboronic acid
afforded the 2-(4-methylphenyl)-6H-dibenzo[b,d]pyran-6-one 8
in high yield.
6
0
two controll experiments were carried out. Firstly, benzoquinone
1
5
was obtained in 61 % H NMR yield when hydroquinone 2a
o
was treated with PhI=O (200 mol%) at 90 C in the mixture of
acetone and DCE for 10 min (eqn 1). Secondly, the product 2-
hydroxy-6H-dibenzo[b,d]pyran-6-one 3a was produced in 99%
yield when the reaction of N-methoxybenzamide 1a with quinone
5
was performed under the standard conditions in the absence of
oxidant (eqn 2). These results indicate that the quinone 5 could be
produced under the standard conditions and servers as the
coupling partner in this Rh(III)-catalyzed reaction.
Scheme 2 Potential synthetic application of hydroxy-substituted 3a.
On the basis of our above observations and literature
1
5g,16,18
precedent
, a mechanistic pathway is proposed (Scheme 1).
6
5
In summary, we have developed a novel Rh(III)-catalyzed C–
H bond arylation with ready available and inexpensive phenol
First, C–H bond cleavage of 1a occurs to produce a five-
membered rhodacycle intermediate A. Next, coordination of the
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

ChemComm
Page 4 of 4
Pd(II)-catalyzed coupling as key step, see: (e) H. Abe, K. Nishioka,
derivatives for the convenient and direct synthesis of
dibenzo[b,d]pyran-6-ones and benzo[d]naphtho[1,2-b]pyran-6-
ones. In this process, benzoquinone derivatives were generated in
situ and used as coupling partner to form both C–C and C–O
bonds. The reaction features high efficiency, atom- and step-
economy, broad substrate scope and good functional-group
tolerance. In addition, the hydroxyl group attached to the
products can be used as a handle for further transformation. The
application of this reaction are being carried out in our laboratory.
Financial supports of this research provided by the NNSFC
S. Takeda, M. Arai, Y. Takeuchi and T. Harayama, Tetrahedron
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7
7
8
8
9
9
0
5
0
5
0
5
and F. J. Fananas, Eur. J. Org. Chem., 2007, 62, 69; by oxidative
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(i) I. Suzuki, M. Wakayama, A. Shigenaga, H. Nemoto and M.
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5
1
0
(21172030) is greatly acknowledged.
Notes and references
1
2
3
For reviews, see: (a) H. N. Lv, P. F. Tu and Y. Jiang, Mini. Rev. Med.
Chem., 2014, 14, 603; (b) Z. Mao, W. Sun, L. Fu, H. Luo, D. Lai
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and D. G. Roux, Phytochemistry, 1983, 22, 2813.
2
008, 10, 2195.
11 For selected recent reviews on C–H bond functionalization, see: (a) Y.
Segawa, T. Maekawa and K. Itami, Angew. Chem. Int. Ed., 2014, 53,
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2
2
3
3
4
4
5
5
6
6
5
0
5
0
5
0
5
0
5
0
5
9
58, Special Issue 6 “C–H Functionalization’’; (c) L. Ackermann, A.
R. Kapdi, H. K. Potukuchi and S. I. Kozhushkov, in Handbook of
Green Chemistry, ed. C.-J. Li, Wiley-VCH, Weinheim. 2012, pp.
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2
59–305; (d) L. Ackermann, Chem. Rev., 2011, 111, 1315; (e) C. S.
1
0322; (b) H. Abe, T. Fukumoto, Y. Takeuchi and T. Harayama,
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4
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and P. Langer, Chem. Eur. J., 2006, 12, 1221; (b) B. I. Alo, A.
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2
010, 110, 575–1211, Special Issue 2 ‘‘Selective Functionalization
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6
For total synthesis altenuisol, see: G. Nemecek, J. Cudaj and J.
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of C–H Bonds’’.
1
1
1
1
1
1
1
1
00 12 For a review on C–H bond arylations with phenols, see: S. I.
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1
3
L. Ackermann, J. Pospech and H. K. Potukuchi, Org. Lett., 2012, 14,
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16, 1004; for Synthesis of Defucogilvocarcin M, see: (c) I.
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4
5, 31; (c) T. Satoh and M. Miura, Chem. Eur. J., 2010, 16, 11212;
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7
8
10
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